Preparation method of hydrophilic anti-fouling HDPE (high-density polyethylene) composite antibacterial pipe

Abstract

The invention discloses a preparation method of a hydrophilic anti-fouling HDPE (high-density polyethylene) composite antibacterial pipe, and belongs to the field of polymer composite material processing. The composite antibacterial pipe is prepared by taking high-density polyethylene, an ethylene-vinyl alcohol copolymer, an EVA-g-MAH compatilizer, a ZnO-TCS antibacterial agent and Span 40 as raw materials through melt mixing, crushing, drying and injection molding. The preparation process is simple, the cost is low, and the obtained composite antibacterial pipe has the characteristics of excellent antibacterial performance, high strength and the like, can be widely applied to the fields of life, industrial water delivery pipelines and the like, and has remarkable economic value and social benefit.

Description

Technical Field

[0001] The invention belongs to the field of polymer composite material processing, and specifically relates to a method for preparing a hydrophilic antifouling HDPE composite antibacterial pipe. Background Art

[0002] High-density polyethylene is a highly crystalline, non-polar thermoplastic resin with good heat resistance and cold resistance, good chemical stability and good mechanical strength. It is widely used in films, pipes, various hollow products, injection molded products, fibers and other material fields. However, when using high-density polyethylene as a pipe, it needs to have stronger anti-fouling and antibacterial properties and mechanical properties under specific working conditions. In order to further make polyethylene pipes more widely used in life and production, and to improve the antibacterial and hydrophilic properties of polyethylene pipes, it is required that the antibacterial agent and hydrophilic agent have sufficiently good compatibility and dispersibility with the matrix.

[0003] Zinc oxide antimicrobial agent is a material with multiple antimicrobial mechanisms. Zinc oxide can generate highly active photogenerated electrons and holes under light conditions, especially ultraviolet light. These photogenerated holes can excite oxygen in the air to become active oxygen, have extremely strong chemical activity, and can undergo oxidation reactions with a variety of microorganisms, thereby killing bacteria. The zinc ion dissolution mechanism is also an important part of the antibacterial effect of zinc oxide. Zinc oxide can slowly release zinc ions in an aqueous medium. These zinc ions bind to the bacterial cell membrane, destroy the structure of membrane proteins, and make them inactive, thereby achieving the purpose of sterilization. In addition, the generation of active oxygen is related to light. Based on the semiconductor properties of zinc oxide, light will lead to the generation of free electrons and electron holes, and then generate active oxygen groups, which connects the active oxygen antibacterial of zinc oxide with the photocatalytic antibacterial effect.

[0004] Triclosan is a broad-spectrum antibacterial agent, and its antibacterial principle is mainly to inhibit bacterial fatty acid synthesis. Triclosan has killing and inhibitory effects on a variety of Gram-positive bacteria, Gram-negative bacteria, fungi and viruses, so its application field is very wide, including toothpaste, soap, facial cleanser, hand sanitizer and other personal care products, as well as medical device disinfectants, wound disinfectants, etc.

[0005] Span 40, also known as sorbitan palmitate, is a nonionic surfactant with emulsifying, thickening and dispersing properties. It is a light yellow granular solid at room temperature with a melting point of about 46-47°C. Its hydrophilicity mainly comes from the polyhydroxy structure in the molecule, which can form hydrogen bonds with water molecules, thereby providing a certain degree of hydrophilicity. At the same time, its molecular structure also contains a long hydrophobic fatty acid chain, so it also has good compatibility with plastics. Summary of the invention

[0006] In view of the problem that the existing high-density polyethylene pipes obtained by injection molding have poor strength and do not have any antibacterial ability, the present invention provides a method for preparing a hydrophilic and anti-fouling HDPE composite antibacterial pipe, which adds a ZnO-TCS antibacterial agent. On the one hand, by combining zinc oxide with triclosan, it can not only take into account the stability of the zinc oxide inorganic antibacterial agent and the excellent antibacterial properties of triclosan, but also the zinc oxide can form a nano-sea island structure to enhance the mechanical properties of the pipe; on the other hand, since Span 40 contains a large number of hydroxyl groups and relatively suitable hydrophobic chains, this can not only ensure the hydrophilicity of the material, but also take into account the compatibility with polyethylene materials, so that the hydrophilicity and strength of the polyethylene pipe can be improved at the same time.

[0007] To achieve the above object, the present invention adopts the following technical solution: A hydrophilic antifouling HDPE composite antibacterial pipe is prepared from high-density polyethylene, ethylene-vinyl alcohol copolymer, EVA-g-MAH compatibilizer, ZnO-TCS antibacterial agent and Span 40 as raw materials through melt mixing, crushing, drying and injection molding.

[0008] The raw materials are calculated by weight as follows: 100 parts of high-density polyethylene, 4 parts of ethylene-vinyl alcohol copolymer, 2 parts of EVA-g-MAH compatibilizer, 1-2 parts by weight of ZnO-TCS antibacterial agent, and 2.5-3.5 parts of Span 40.

[0009] Furthermore, the model of the high-density polyethylene is 5000S, and its density is 0.941-0.960 g / cm 3 .

[0010] Furthermore, the model of the ethylene-vinyl alcohol copolymer is EW-3801.

[0011] Furthermore, the model of the EVA-g-MAH compatibilizer is Bynel 39E660.

[0012] Furthermore, the preparation method of the ZnO-TCS antibacterial agent comprises the following steps: (1) Accurately weigh 1g zinc oxide and add it to 60ml ethanol solution with a volume concentration of 99%, then add 20ml pure water and 1ml silane coupling agent KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH value to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan (TCS) powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly add 0.7 ml of methacrylic anhydride, then add 0.3 g of 4-dimethylaminopyridine (DMAP) powder, and finally add 1 M NaOH solution to adjust the pH value to about 9. React for 6 h in an oil bath at 60°C and 600 r / min. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, pass nitrogen for 30 min, then add 0.5 g of azobisisobutylimidazoline hydrochloride (AIBI) powder, react under oil bath conditions of 55°C and 600 r / min for 10 h, and finally centrifuge, wash, and freeze-dry to obtain the ZnO-TCS antibacterial agent.

[0013] Furthermore, the melt mixing is carried out in a torque rheometer at 200° C. and 100 r / min for 9 to 10 min.

[0014] Furthermore, the injection molding is performed in a micro injection molding machine at 220° C. and a pressure of 0.3-0.5 MPa for 10 seconds and holding the pressure for 5 seconds.

[0015] The beneficial effects of the present invention are: (1) The antibacterial effect of zinc oxide requires a light environment, and the antibacterial effect is poor in the absence of light. The present invention prepares the ZnO-TCS antibacterial agent by grafting the organic antibacterial agent triclosan onto the inorganic antibacterial agent zinc oxide. In the process, the carbon-carbon double bond of TCS-MA is polymerized with the carbon-carbon double bond of ZnO-KH570 to form a highly stable carbon-carbon single bond. On the one hand, this allows the obtained antibacterial agent to have the high stability and high temperature resistance of the inorganic antibacterial agent, and on the other hand, it allows the obtained antibacterial agent to have excellent antibacterial effect in the absence of light. In addition, since the antibacterial agent is obtained by modifying zinc oxide as the matrix, it can act as an island structure in polyethylene, which greatly improves the strength of the composite material.

[0016] (2) In the process of preparing the ZnO-TCS antibacterial agent of the present invention, KH570 is grafted onto zinc oxide to insert a double bond. At the same time, based on the characteristics of triclosan having independent phenolic hydroxyl groups and methacrylic anhydride having high esterification reaction ability, triclosan and methacrylic anhydride are subjected to an esterification reaction to graft a double bond onto triclosan. Finally, the ZnO-TCS antibacterial agent obtained by the polymerization reaction of carbon-carbon double bonds can take into account the high stability of zinc oxide and the broad-spectrum antibacterial properties of triclosan, and can effectively kill and inhibit a variety of Gram-positive bacteria, Gram-negative bacteria, molds, yeasts and viruses.

[0017] (3) Ethylene-vinyl alcohol copolymer is an olefin thermoplastic with the advantages of high strength, strong thermal stability, high barrier properties and excellent hydrophilic properties. The present invention adds ethylene-vinyl alcohol copolymer to polyethylene, which can solve the problem of poor barrier properties and hydrophilic properties of polyethylene. At the same time, the present invention adopts a high-temperature melt blending process to evenly disperse the ethylene-vinyl alcohol copolymer in polyethylene. In addition, since the crystallization temperature of ethylene-vinyl alcohol copolymer is different from that of high-density polyethylene, an island particle structure can be formed inside the polyethylene material during the crystallization process, further improving the mechanical properties of the material.

[0018] (4) The advantages of Span 40 as a hydrophilic agent are mainly reflected in the following aspects: First, Span 40 is amphiphilic, which not only makes it have good hydrophilic properties, but also has good compatibility with polyethylene materials. In addition, the carbon chain length of Span 40 is 16 carbon atoms, which not only ensures its hydrophilic properties in the small molecule state, but also ensures its high temperature stability during plastic processing.

[0019] (5) The preparation process of the present invention is simple and low in cost. The obtained composite antibacterial pipe has the characteristics of excellent antibacterial performance and high strength. It can be widely used in the fields of domestic and industrial water pipelines, and has significant economic value and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The infrared absorption spectra of ZnO-KH570 and ZnO-TCS prepared in Example 1 are shown.

[0021] Figure 2 This is the infrared absorption spectrum of TCS-MA prepared in Example 1.

[0022] Figure 3 This is a cross-sectional morphology diagram of the composite antibacterial tubing prepared in Example 1.

[0023] Figure 4 This is a cross-sectional morphology diagram of the high-density polyethylene pipe prepared in Comparative Example 1. DETAILED DESCRIPTION

[0024] A hydrophilic antifouling HDPE composite antibacterial pipe, the preparation of which comprises the following steps: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH value to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH value to about 9. React for 6 h in an oil bath at 60°C and 600 r / min. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the TCS-MA powder prepared in step (2), add it to 40 ml of 99% ethanol solution, then add 1 g of the ZnO-KH570 powder prepared in step (1), flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react for 10 h in an oil bath at 55°C and 600 r / min, and finally centrifuge and wash, and freeze-dry to obtain a ZnO-TCS antibacterial agent; (4) By weight, 100 parts of high-density polyethylene, 4 parts of ethylene-vinyl alcohol copolymer, 2 parts of EVA-g-MAH compatibilizer, 1-2 parts by weight of ZnO-TCS antibacterial agent, and 2.5-3.5 parts of Span 40 were added to a torque rheometer and mixed at 200°C and 100 r / min for 9-10 min. After that, they were crushed and dried in a vacuum drying oven overnight. Then, they were added to a micro injection molding machine and pressed at 220°C and a pressure of 0.3-0.5 MPa for 10 s and maintained at pressure for 5 s.

[0025] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0026] The high-density polyethylene used in the examples is 5000S, and its density is 0.941-0.960 g / cm 3 The model of the ethylene-vinyl alcohol copolymer used is EW-3801. The model of the EVA-g-MAH compatibilizer used is Bynel 39E660.

[0027] Example 1 The preparation steps of hydrophilic antifouling HDPE composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS powder; (4) According to weight, 100 parts of high-density polyethylene, 1.5 parts of ZnO-TCS antibacterial agent, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a drying oven at 60°C overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a hydrophilic and anti-fouling HDPE composite antibacterial pipe.

[0028] Figure 1 The infrared absorption spectra of ZnO-KH570 and ZnO-TCS prepared in this example are shown in the figure. -1 and 1635 cm -1 The absorption peaks of the carbon-carbon double bond and the Si-O bond correspond to the absorption peaks of the carbon-carbon double bond. By comparing ZnO, it can be seen that the silane coupling agent was successfully grafted onto ZnO and a carbon-carbon double bond was introduced. By comparing ZnO-KH570 and ZnO-TCS, it can be found that the absorption peak of the carbon-carbon double bond in ZnO-TCS disappeared, indicating that the polymerization reaction caused the carbon-carbon double bond to polymerize into a carbon-carbon single bond. At the same time, the absorption peak of ZnO-TCS at 1475 cm -1 and 1748 cm -1 The absorption peaks of benzene ring and ester group appear at the bottom of the graphite layer. Since ZnO-KH570 itself does not have benzene ring and ester group, it shows that zinc oxide has been successfully grafted with triclosan.

[0029] Figure 2 The infrared absorption spectrum of TCS-MA prepared in this example is shown in the figure. -1The absorption peak of triclosan corresponds to the stretching vibration absorption peak of C-Cl, which indicates that the antibacterial functional group is not damaged during the grafting of triclosan with methacrylic anhydride; triclosan has an absorption peak of 3310 cm -1 The corresponding hydroxyl stretching vibration absorption peak at 2930 cm -1 The stretching vibration absorption peak of methyl group appeared at 1635 cm -1 and 1748 cm -1 The corresponding absorption peaks are carbon-carbon double bond and carbon-oxygen bond, respectively, indicating that TCS-MA has been successfully grafted with carbon-carbon double bond through esterification reaction.

[0030] Figure 3 This is a cross-sectional morphology diagram of the composite antibacterial tube prepared in this embodiment. As shown in the figure, a large number of wire drawing morphologies and granular substances appear on the cross section of the material, indicating that the toughness of the composite material is enhanced and the overall dispersion of ZnO-TCS is excellent.

[0031] Example 2 The preparation steps of hydrophilic antifouling HDPE composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS powder; (4) According to weight, 100 parts of high-density polyethylene, 1 part of ZnO-TCS antibacterial agent, 3.5 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a drying oven at 60°C overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a hydrophilic and anti-fouling HDPE composite antibacterial pipe.

[0032] Example 3 The preparation steps of hydrophilic antifouling HDPE composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS powder; (4) According to weight, 100 parts of high-density polyethylene, 2 parts of ZnO-TCS antibacterial agent, 2.5 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a drying oven at 60°C overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and stamped at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a hydrophilic and anti-fouling HDPE composite antibacterial pipe.

[0033] Comparative Example 1 The preparation steps of high-density polyethylene pipe are as follows: 100 parts by weight of high-density polyethylene were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a drying oven at 60°C overnight, and then the obtained powder was added to a micro injection molding machine, the mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 seconds, and the pressure was maintained for 5 seconds to obtain a high-density polyethylene pipe.

[0034] Figure 4 This is a cross-sectional morphology diagram of the high-density polyethylene pipe prepared in this comparative example. As can be seen from the figure, there is no obvious wire drawing state and particles in its cross section.

[0035] Comparative Example 2 The preparation steps of HDPE composite pipe are as follows: By weight, 100 parts of high-density polyethylene, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a drying oven at 60°C overnight, and then added into a micro injection molding machine. The mold temperature was set to 55°C, and punched for 10 seconds at 220°C and a pressure of 0.4 MPa, and the pressure was maintained for 5 seconds to obtain a HDPE composite pipe.

[0036] Comparative Example 3 The preparation steps of HDPE composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS powder; (4) According to weight, 100 parts of high-density polyethylene, 1.5 parts of ZnO-TCS antibacterial agent, 3 parts of Span 40 and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a drying oven at 60°C overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and punched at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a HDPE composite antibacterial pipe.

[0037] Comparative Example 4 The preparation steps of HDPE composite antibacterial pipe are as follows: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly drop 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH to about 9. React at 60°C, 600 r / min oil bath conditions for 6 h. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of the prepared TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, flow nitrogen for 30 min, then add 0.5 g of AIBI powder, react under oil bath conditions of 55 °C and 600 r / min for 10 h, finally centrifuge and wash, and freeze-dry to obtain ZnO-TCS powder; (4) According to weight, 100 parts of high-density polyethylene, 1.5 parts of ZnO-TCS antibacterial agent, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 min, crushed and dried in a drying oven at 60°C overnight, and then added to a micro injection molding machine. The mold temperature was set to 55°C, and stamped at 220°C and a pressure of 0.4 MPa for 10 s, and the pressure was maintained for 5 s to obtain a HDPE composite antibacterial pipe.

[0038] Comparative Example 5 The preparation steps of hydrophilic antifouling HDPE composite antibacterial pipe are as follows: By weight, 100 parts of high-density polyethylene, 1.5 parts of ZnO antibacterial agent, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a drying oven at 60°C overnight, and then added into a micro injection molding machine, the mold temperature was set to 55°C, and punched for 10 seconds at 220°C and a pressure of 0.4 MPa, and the pressure was maintained for 5 seconds to obtain a HDPE composite antibacterial pipe.

[0039] Comparative Example 6 The preparation steps of HDPE composite antibacterial pipe are as follows: By weight, 100 parts of high-density polyethylene, 1.5 parts of TCS antibacterial agent, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a drying oven at 60°C overnight, and then added into a micro injection molding machine, the mold temperature was set to 55°C, and punched for 10 seconds at 220°C and a pressure of 0.4 MPa, and the pressure was maintained for 5 seconds to obtain a HDPE composite antibacterial pipe.

[0040] Comparative Example 7 The preparation steps of HDPE composite antibacterial pipe are as follows: By weight, 100 parts of high-density polyethylene, 1 part of ZnO, 0.5 part of TCS, 3 parts of Span 40, 2 parts of EVA-g-MAH compatibilizer and 4 parts of ethylene-vinyl alcohol copolymer were put into a torque rheometer, mixed at 200°C and 100 r / min for 9 minutes, crushed and dried in a drying oven at 60°C overnight, and then added into a micro injection molding machine, the mold temperature was set to 55°C, and punched for 10 seconds at 220°C and a pressure of 0.4 MPa, and the pressure was maintained for 5 seconds to obtain a HDPE composite antibacterial pipe.

[0041] The finished products prepared in the embodiments and comparative examples were tested for antibacterial properties according to GB / T 20944.3-2008; the water contact angle was tested according to GB / T30693-2014; the bending strength was tested according to the test method of GB / T 9341-2008; the impact strength was tested according to the test method of ISO179-1:2000; the tensile strength and elongation at break were tested according to the test method of GB / T 1040.2-2006, and the results are shown in Table 1.

[0042] Table 1 Performance test results

[0043] From the results in Table 1, it can be seen that compared with the materials obtained in the comparative examples, the antibacterial properties and strength of the materials prepared in the examples are greatly improved, proving that the prepared HDPE composite pipe has excellent antibacterial properties and can achieve improved mechanical properties. Among them, the HDPE composite antibacterial pipe prepared in Example 1 has the most excellent hydrophilic antifouling properties and mechanical properties.

[0044] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A method for preparing a hydrophilic antifouling HDPE composite antibacterial pipe, characterized in that: The hydrophilic antifouling HDPE composite antibacterial pipe is prepared by using high-density polyethylene, ethylene-vinyl alcohol copolymer, EVA-g-MAH compatibilizer, ZnO-TCS antibacterial agent and Span 40 as raw materials through melt mixing, crushing, drying and injection molding.

2. The method for preparing the hydrophilic antifouling HDPE composite antibacterial pipe according to claim 1, characterized in that: The raw materials are calculated by weight as follows: 100 parts of high-density polyethylene, 4 parts of ethylene-vinyl alcohol copolymer, 2 parts of EVA-g-MAH compatibilizer, 1-2 parts by weight of ZnO-TCS antibacterial agent, and 2.5-3.5 parts of Span 40.

3. The method for preparing the hydrophilic antifouling HDPE composite antibacterial pipe according to claim 1 or 2, characterized in that: The model of the high-density polyethylene is 5000S, and its density is 0.941-0.960 g / cm 3 .

4. The method for preparing the hydrophilic antifouling HDPE composite antibacterial pipe according to claim 1 or 2, characterized in that: The model of the ethylene-vinyl alcohol copolymer is EW-3801.

5. The method for preparing the hydrophilic antifouling HDPE composite antibacterial pipe according to claim 1 or 2, characterized in that: The model of the EVA-g-MAH compatibilizer is Bynel 39E660.

6. The method for preparing the hydrophilic antifouling HDPE composite antibacterial pipe according to claim 1 or 2, characterized in that: The preparation method of the ZnO-TCS antibacterial agent comprises the following steps: (1) Accurately weigh 1g zinc oxide and add it to 60ml 99% ethanol solution, then add 20ml pure water and 1ml KH570, stir until completely dissolved in a water bath at 60℃ and 600r / min, then slowly add glacial acetic acid to the solution to adjust the pH value to 4, react for 2h, and finally centrifuge and wash, and freeze-dry to obtain ZnO-KH570 powder; (2) Accurately weigh 1 g of triclosan powder, add it to 80 ml of pure water, heat it to 60°C and stir until it is completely dissolved, then slowly add 0.7 ml of methacrylic anhydride, then add 0.3 g of DMAP powder, and finally add 1 M NaOH solution to adjust the pH value to 9. React for 6 h in an oil bath at 60°C and 600 r / min. After the reaction is completed, centrifuge, wash, and freeze-dry to obtain TCS-MA powder; (3) Accurately weigh 0.5 g of TCS-MA powder and add it to 40 ml of 99% ethanol solution, then add 1 g of the prepared ZnO-KH570 powder, pass nitrogen for 30 min, then add 0.5 g of AIBI powder, react for 10 h in an oil bath at 55°C and 600 r / min, and finally centrifuge, wash, and freeze-dry to obtain the ZnO-TCS antibacterial agent.

7. The method for preparing the hydrophilic antifouling HDPE composite antibacterial pipe according to claim 1, characterized in that: The melt mixing is carried out in a torque rheometer at 200° C. and 100 r / min for 9 to 10 min.

8. The method for preparing the hydrophilic antifouling HDPE composite antibacterial pipe according to claim 1, characterized in that: The injection molding is carried out in a micro injection molding machine at 220° C. and a pressure of 0.3-0.5 MPa for 10 seconds and holding the pressure for 5 seconds.

9. A hydrophilic, anti-fouling HDPE composite antibacterial pipe prepared by the method of claim 1.

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